TW201942214A - Method for manufacturing molded article and preform of molded article - Google Patents

Abstract

Provided is a method for manufacturing molded articles having excellent stiffness and lightness, and improved design and liquid-repellency by means of a simple process. The present invention is a method for manufacturing a molded article in which a thin film layer (B) is formed on the surface of a porous body (A), and involves performing the following steps (I)-(II) in the following order. Step (I): a step for obtaining a preform by forming the thin film layer (B) on the surface of a precursor (a) of the porous body (A). Step (II): a step for expanding the precursor (a) to mold the precursor on the porous body (A).

Description

   Manufacturing method of shaped article and preform of shaped article   

The present invention relates to a method for manufacturing a molded article having excellent designability and liquid repellency, and a preform of the molded article.

In recent years, fiber-reinforced composite materials that reinforce fiber and matrix resin have been widely used as industrial products such as automobiles, airplanes, and sports products as structures that improve mechanical properties and light weight. A product using a fiber-reinforced composite material is applied by coating or the like for the purpose of imparting design or liquid repellency. As a technique for forming a coating layer on a fiber-reinforced composite material, it is proposed to heat a preform having a resin layer composed of a thermosetting resin and a solid additive on the prepreg layer to heat the matrix resin and A technique for curing a thermosetting resin of a resin layer to form a resin cured layer having a predetermined thickness (for example, refer to Patent Document 1).

On the other hand, for the purpose of reducing the weight of fiber-reinforced composite materials, proposals have been made for structures that have predetermined mechanical properties and are made of resin, reinforcing fibers, and voids (for example, refer to Patent Document 2). When a coating layer is provided on a structure having continuous voids in the thickness direction for design purposes or the like, the material constituting the coating layer penetrates and there is a problem that the target coating layer cannot be obtained.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 2016-78451

Patent Document 2: Japanese Patent No. 6123965

Patent Document 3: International Publication No. 2015/029634

Patent Document 4: Japanese Patent Laid-Open No. 52-115875

Although a technique of providing a skin material on the surface of a porous body or patterning with ink is also proposed (for example, refer to Patent Documents 3 and 4), the purpose of the skin layer of Patent Document 3 is to improve the rigidity of the core layer having voids. In view of design, it is necessary to further provide a coating layer. In addition, because the skin layer is a prepreg in which a reinforcing fiber is impregnated with a matrix resin, the preparation of the prepreg layer is time-consuming, and because the core layer and the skin layer are not bonded in the previous step of the porous body forming step, Therefore, it is necessary to laminate a core layer and a skin layer to a desired structure during molding. On the other hand, since Patent Document 4 is a porous body using a foaming agent, the voids are discontinuous, and the problem is not the penetration of the material.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a method for manufacturing a molded article and a molded article that are excellent in rigidity and light weight, have improved designability or liquid repellency, and can be molded into a molded product in a simple procedure. Prefab.

The method for manufacturing a molded article of the present invention is characterized in that it is a method for manufacturing a molded article in which a thin film layer (B) is formed on the surface of a porous body (A), and is carried out in the order of the following steps (I) to (II): steps (I): a step of obtaining the preform by forming the thin film layer (B) on the surface of the precursor (a) of the porous body (A); step (II): expanding the precursor (a) to form The step of the porous body (A).

Furthermore, the present invention is a preform of a molded article forming a thin film layer (B) on the surface of a porous body (A) containing reinforcing fibers (A1), resin (A2), and voids (A3); The precursor (a) of the porous body (A) and the thin film layer (B) on the surface of the precursor (a), and the thin film layer (B) is in accordance with JIS K5600-5-6 (1999). The adhesion properties of the aforementioned precursor (a) belong to classifications 0 to 3.

According to the method for manufacturing a molded article and the preform of the molded article of the present invention, since the thin film layer is formed in the precursor (a) state of the porous body (A), the thin film layer (B) does not penetrate into the porous body (A In the case of continuous porosity), a molded product excellent in both design and liquid repellency can be obtained while maintaining lightweight. In addition, since it is not necessary to consider infiltration, there are many choices of materials for forming the thin film layer (B), and the degree of design freedom is improved. In addition, even if the step (II) and the step (I) of the forming step are carried out in different places, it is not necessary to laminate the precursor (a) of the porous body (A) and the thin film layer (B), and the like can be simplified. Manufacture of molded articles.

1‧‧‧ reinforced fiber

1a ~ 1f‧‧‧Single fiber

2‧‧‧ secondary element alignment angle

3‧‧‧mould

3A‧‧‧Up mold

3B‧‧‧ Lower mold

4‧‧‧ Precursor (a)

5‧‧‧ film layer (B)

1 (a) and 1 (b) are schematic views showing an example of the dispersed state of the reinforcing fibers of the reinforcing fiber felt of the present invention.

Fig. 2 is a schematic view showing an example of an apparatus for manufacturing a reinforced fiber felt according to the present invention.

Fig. 3 is an explanatory view of the production of a molded article of the present invention.

4 (a) and 4 (b) are explanatory diagrams for manufacturing a molded article of the present invention.

Hereinafter, the manufacturing method of the molded article of this invention is demonstrated.

The method for manufacturing a molded article of the present invention is characterized in that it is a method for manufacturing a molded article in which a thin film layer (B) is formed on the surface of a porous body (A), and is carried out in the order of the following steps (I) to (II): steps (I): a step of obtaining a preform by forming a thin film layer (B) on the surface of the precursor (a) of the porous body (A); step (II): expanding the precursor (a) to form the porous body (A).

    (Porous body (A))    

In the molded article of the present invention, the porous body (A) contains reinforcing fibers (A1), resin (A2), and voids (A3).

唑)、聚苯硫醚、聚酯、丙烯酸、尼龍、聚乙烯等有機纖維；碳化矽、氮化矽等無機纖維。又，亦可對該等纖維施行表面處理。表面處理係除利用導電體金屬進行的被黏處理之外，尚有利用偶合劑施行的處理、利用上漿劑施行的處理、利用集束劑施行的處理、利用添加劑施行的附著處理等。又，該等纖維係可單獨使用1種、亦可併用2種以上。其中，從輕量化效果的觀點，較佳係使用比強度、比剛性優異的PAN系、瀝青系、縲縈系等碳纖維。又，從提高所獲得多孔質體(A)之經濟性的觀點，較佳係使用玻璃纖維，特別係從力學特性與經濟性均衡的觀點，較佳係併用碳纖維與玻璃纖維。又，從提高所獲得多孔質體(A)的衝擊吸收性或塑形性的觀點，較 佳係使用聚芳醯胺纖維，特別係從力學特性與衝擊吸收性均衡的觀點，較佳係併用碳纖維與聚芳醯胺纖維。又，從提高所獲得多孔質體(A)之導電性的觀點，亦可使用由具導電性之金屬所構成的金屬纖維，或經鎳、銅、鐿等金屬被覆的強化纖維。該等之中，更佳係使用從強度與彈性模數等力學特性優異的金屬纖維、瀝青系碳纖維、及PAN系碳纖維所構成群組中選擇的強化纖維。 In the porous body (A) of the present invention, the reinforcing fibers (A1) are exemplified by metal fibers such as aluminum, brass, and stainless steel; PAN-based, fluorene-based, lignin-based, pitch-based carbon fibers, graphite fibers, and glass Insulating fiber; polyaramide, PBO (polybenzo

Azole), polyphenylene sulfide, polyester, acrylic, nylon, polyethylene and other organic fibers; silicon carbide, silicon nitride and other inorganic fibers. The fibers may also be surface-treated. The surface treatment is a treatment using a conductive metal, a treatment using a coupling agent, a treatment using a sizing agent, a treatment using a sizing agent, and an adhesion treatment using an additive. These fibers may be used alone or in combination of two or more. Among them, from the viewpoint of weight reduction effects, it is preferable to use carbon fibers such as PAN-based, pitch-based, and fluorene-based, which are excellent in specific strength and specific rigidity. From the viewpoint of improving the economics of the obtained porous body (A), it is preferable to use glass fiber, and particularly from the viewpoint of balancing mechanical properties and economy, it is more preferable to use carbon fiber and glass fiber together. From the viewpoint of improving the impact absorption or shapeability of the obtained porous body (A), it is preferable to use polyaramide fiber, and it is particularly preferable to use it in combination from the viewpoint of balancing mechanical properties and impact absorption. Carbon fiber and polyamide fiber. From the viewpoint of improving the conductivity of the obtained porous body (A), a metal fiber composed of a conductive metal or a reinforcing fiber coated with a metal such as nickel, copper, or rhenium may also be used. Among these, it is more preferable to use reinforcing fibers selected from the group consisting of metal fibers, pitch-based carbon fibers, and PAN-based carbon fibers that are excellent in mechanical properties such as strength and elastic modulus.

The reinforcing fibers (A1) are preferably discontinuous and randomly dispersed in the porous body (A). In addition, it is more preferable that the dispersed state is slightly monofilament. By setting the reinforcing fiber (A1) in such a state, when external force is applied to the precursor (a) or porous body (A) of the sheet-like porous body (A), it can be easily molded into a complex shape. shape. In addition, by setting the reinforcing fibers (A1) in such a state, the voids (A3) formed by the reinforcing fibers (A1) are densified, and the fiber bundles of the reinforcing fibers (A1) in the porous body (A) are densified. The weak end can be minimized, so in addition to excellent reinforcement efficiency and reliability, it also gives isotropy.

The "slightly monofilament-like" herein refers to the existence of fine-grained strands with less than 500 monofilaments of reinforcing fibers. It is more preferably monofilament-like, that is, a state in which monofilaments are dispersed.

Here, the "slightly monofilament-like" or "dispersed monofilament-like" refers to a single fiber whose secondary element alignment angle is 1 ° or more among the reinforcing fibers (A1) arbitrarily selected in the porous body (A). The ratio (hereinafter also referred to as the "fibre dispersion rate") is 80% or more, in other words, the parallel body in the porous body (A) that is contacted by two or more single fibers is less than 20%. Therefore, it is particularly preferable that the mass fraction of the fiber bundles having at least 100 filaments among the reinforcing fibers (A1) is 100%.

Furthermore, it is more preferable that the reinforcing fibers (A1) are randomly dispersed. Here, the "reinforcement fibers (A1) are randomly dispersed" refers to a range in which the arithmetic mean value of the secondary element alignment angles of the reinforcement fibers (A1) arbitrarily selected in the porous body (A) is 30 ° or more and 60 ° or less Inside. The "two-dimensional alignment angle" refers to an angle formed by a single fiber of a reinforcing fiber (A1) and a single fiber intersecting with the single fiber, and is defined as an angle formed by the intersecting single fibers with each other at 0 ° The angle on the acute angle side in the range from 90 ° to 90 °.

This secondary element alignment angle will be described in more detail using drawings. In FIGS. 1 (a) and (b), when the single fiber 1 a is used as a reference, the single fiber 1 a intersects with other single fibers 1 b to 1 f. Here, the term "cross" refers to the state where the single fiber used as a reference and other single fibers are crossed in the observed two-dimensional plane, and the single fibers 1a and 1b ~ 1f do not necessarily have to be in contact. It is not an exception to observe the state of crossing when viewing. In other words, when the single fiber 1a serving as a reference is viewed, all the single fibers 1b to 1f are the evaluation objects of the two-dimensional alignment angle. In FIG. The angle on the acute angle side in the range of 0 ° to 90 °.

The method of measuring the two-dimensional alignment angle is not particularly limited, and examples thereof include a method of observing the alignment of the reinforcing fibers (A1) from the surface constituting the requirements. The average value of the two-dimensional alignment angle is measured in the following procedure. That is, the average value of the two-dimensional alignment angles of randomly selected single fibers (single fibers 1a in FIG. 1) and all intersecting single fibers (single fibers 1b to 1f in FIG. 1) is measured. For example, when there are many other single fibers crossed by a single fiber, the other single fibers crossed may also be substituted with randomly selected 20 counted arithmetic average values. This measurement is performed 5 times with other single fibers as the basis weight composite meter, and then the arithmetic mean is calculated and set as the arithmetic mean of the two-dimensional alignment angle.

When the reinforcing fibers (A1) are slightly monofilament-like and randomly dispersed, the performance imparted by the above-mentioned reinforcing fibers (A1) dispersed in a substantially monofilament-like state can be maximized. In addition, the porous body (A) can be made isotropic in mechanical properties. From this viewpoint, the fiber dispersion rate of the reinforcing fibers (A1) is preferably 90% or more, and the closer to 100%, the better. The arithmetic mean value of the two-dimensional alignment angle of the reinforcing fiber (A1) is preferably in a range of 40 ° or more and 50 ° or less, and the closer to the ideal angle 45 °, the better. A preferable range of the two-dimensional alignment angle is that any one of the above upper limits may be set as the upper limit, and any one of the above lower limits may be set as the lower limit.

On the other hand, examples of the form in which the reinforcing fibers (A1) are not discontinuous include a sheet substrate, a fabric substrate, and a non-crimp substrate in which the reinforcing fibers (A1) are aligned in a single direction. Since the reinforcing fibers (A1) in these forms are regularly and densely arranged, the voids (A3) in the porous body (A) are reduced, and the impregnation of the resin (A2) is extremely difficult, and an unimpregnated portion or an impregnation may be formed. In cases where the choice of method and resin type is greatly restricted.

The form of the reinforcing fibers (A1) can be either continuous reinforcing fibers of the same length as the porous body (A), or discontinuous reinforcing fibers of limited length cut to a predetermined length. From the viewpoint of easily impregnating the resin (A2) or easily adjusting it, it is preferably a discontinuous reinforcing fiber.

The mass average fiber length of the reinforcing fibers (A1) is preferably within a range of 1 mm to 15 mm. Thereby, the reinforcing efficiency of the reinforcing fiber (A1) can be improved, and excellent mechanical properties can be imparted to the porous body. When the mass average fiber length of the reinforcing fibers (A1) is 1 mm or more, the voids (A3) in the porous body (A) can be formed efficiently, so that the density can be reduced, in other words, the same thickness and light weight can be obtained The porous body (A) is preferred. On the other hand, when the mass average fiber length of the reinforcing fibers (A1) is 15 mm or less, the reinforcing fibers (A1) in the porous body (A) are not easily bent due to their own weight, and the appearance of mechanical properties is not inhibited. good. The mass average fiber length is obtained by removing the resin (A2) component of the porous body (A) by burning or dissolution, and then randomly selecting 400 fibers from the remaining reinforcing fibers (A1), and measuring the length to 10 μm units. These mass average fiber lengths can be calculated.

The reinforcing fiber (A1) is preferably in a non-woven form from the viewpoint of the ease of impregnation of the resin (A2) with the reinforcing fiber (A1). In addition, since the reinforcing fiber (A1) has a non-woven shape, in addition to the ease of handling of the non-woven itself, when it is generally a thermoplastic resin with a high viscosity, it can be easily impregnated, so it is preferable. Here, the "non-woven form" refers to a form in which the irregularities of the strands and / or monofilaments of the reinforcing fibers are dispersed in a plane shape, and examples include cut strand felt, continuous fiber strand felt, papermaking felt, and carding mat ( carding mat), air laid mat (hereinafter collectively referred to as "reinforcing fiber mat").

In the porous body (A) of the present invention, the resin (A2) is exemplified by a thermoplastic resin or a thermosetting resin. The present invention may also incorporate a thermosetting resin and a thermoplastic resin. The resin (A2) is a matrix resin constituting the precursor (a) of the porous body (A) and the porous body (A).

In one aspect of the present invention, the resin (A2) preferably contains at least one thermoplastic resin. Examples of thermoplastic resins are: "Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate Polyesters such as diester (PEN), liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutene; polyoxymethylene (POM), polyamide (PA), polyphenylene sulfide ( PPS) and other polyarylene sulfide; polyketone (PK), polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether nitrile (PEN), polytetrafluoroethylene, etc. Crystalline resins such as fluorine-based resins and liquid crystal polymers (LCP); "styrene-based resins, as well as polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), and polystyrene Ether (PPE), polyimide (PI), polyimide (imide), PAI, polyether (imide), polyether (PSU), polyether (imide), polyarylate (PAR), etc. Amorphous resin; Other examples include: phenol-based resin, phenoxy resin, and polystyrene-based, polyolefin-based, polyurethane-based, polyester-based, polyamide-based, polybutadiene-based, polyisoprene Thermoplastic elastomers such as olefin-based, fluorine-based resins, and acrylonitrile; or copolymers of these And modified resins. Among them, from the viewpoint of the lightness of the obtained porous body (A), polyolefin is preferable, from the viewpoint of strength, polyamine is preferable, and from the viewpoint of surface appearance, polycarbonate or From the viewpoint of heat resistance, polystyrene arylene sulfide is preferred from the viewpoint of heat resistance, and from the viewpoint of continuous use temperature, polyether ether ketone is preferred, and from the viewpoint of resistance, The best series uses fluorine resin.

In one aspect of the present invention, the resin (A2) preferably contains at least one type of thermosetting resin. Examples of thermosetting resins include unsaturated polyesters, vinyl esters, epoxy resins, phenol resins, urea resins, melamine resins, thermosetting polyimide resins, copolymers, modifiers, and blends thereof. A combination of at least two types of resins.

In addition, as long as the object of the present invention is not impaired, the porous body (A) of the present invention is one of the components of the resin (A2), and may also contain an impact resistance improver such as an elastomer or a rubber component, and others. Filler or additive. Examples of fillers or additives include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, shock absorbers, antibacterial agents, insect repellents, deodorants, and anti- Colorants, heat stabilizers, release agents, antistatic agents, plasticizers, slippers, colorants, pigments, dyes, foaming agents, foam suppressants, or coupling agents.

The porous body (A) of the present invention has voids (A3). The "void (A3)" in the present invention refers to a space formed by the reinforcing fibers (A1) covered with the resin (A2) forming a columnar support and overlapping or crossing them. For example, when the precursor (a) of the porous body (A) of the reinforcing fiber (A1) is impregnated with the resin (A2) in advance, and the porous body (A) is obtained by heating, the resin (A2) is melted or softened by heating. The voids (A3) are formed by raising the reinforcing fibers (A1). This phenomenon occurs in the precursor (a) of the porous body (A), in which the internal reinforcing fibers (A1) in a compressed state are pressurized, and fluffing occurs according to the fluffing force derived from the elastic modulus thereof. The void (A3) is continuous at least in the thickness direction.

The porous body (A) of the present invention preferably has a volume content ratio (%) of the reinforcing fiber (A1) of 0.5 to 55% by volume, a volume content ratio (%) of the resin (A2) of 2.5 to 85% by volume, and voids. The volume content rate (%) of (A3) is 10 to 97 volume%.

In the porous body (A), if the volume content rate of the reinforcing fibers (A1) is 0.5% by volume or more, the reinforcing effect derived from the reinforcing fibers (A2) is sufficient, which is preferable. On the other hand, when the volume content rate of the reinforcing fiber (A1) is 55% by volume or less, the volume content rate of the resin (A2) relative to the reinforcing fiber (A1) is relatively increased, and the reinforcing fiber in the porous body (A) is increased. The (A1) is adhered to each other, so that the reinforcing effect of the reinforcing fiber (A1) is sufficient, so it can satisfy the mechanical characteristics of the porous body (A), particularly the bending characteristics, and is therefore preferable.

In the porous body (A), if the volume content of the resin (A2) is 2.5% by volume or more, the reinforcing fibers (A1) in the porous body (A) will adhere to each other, and the strength of the reinforcing fibers (A1) can be increased. The reinforcing effect is sufficient, and it can satisfy the mechanical characteristics of the porous body (A), especially the bending elastic modulus, so it is preferable. On the other hand, if the volume content of the resin (A2) is 85% by volume or less, the formation of the voids (A3) is not hindered, which is preferable.

In the porous body (A), the reinforcing fiber (A1) is coated with the resin (A2), and the thickness (coating thickness) of the coated resin (A2) is preferably within a range of 1 μm to 15 μm. The covering state of the reinforcing fibers covered with the resin (A2) is lifted from the porous body (A) before the single fibers of the reinforcing fibers (A1) constituting the porous body (A) are covered at the intersections of the fibers. The viewpoints of shape stability, ease of thickness control, and degree of freedom are sufficient, and a more preferable state is that the resin (A2) is coated with the reinforcing fiber (A1) around the thickness as described above. In this state, the surface of the reinforcing fiber (A1) is not exposed by the resin (A2). In other words, the reinforcing fiber (A1) is a wire-shaped film formed by the resin (A2). Thereby, the porous body (A) further has shape stability and sufficiently exhibits mechanical properties. In addition, the covering state of the reinforcing fibers (A1) covered with the resin (A2) does not require that all the reinforcing fibers (A1) are covered, as long as the shape stability of the porous body (A) of the present invention is not impaired, Or within the range of bending elastic modulus and bending strength.

In the porous body (A), the volume content rate of the voids (A3) is preferably within a range of 10% by volume to 97% by volume. When the content of the voids (A3) is 10% by volume or more, the density of the porous body (A) can be reduced, so that it is possible to satisfy the lightweight property, which is preferable. On the other hand, if the content of the voids (A3) is 97% by volume or less, in other words, the thickness of the resin (A2) coated around the reinforcing fibers (A1) is sufficient, so that the reinforcing fibers (A1) in the porous body (A) ) It is better to strengthen each other and improve the mechanical characteristics. The upper limit of the volume content rate of the voids (A3) is preferably 97% by volume. In the present invention, the volume content rate refers to a total volume content rate of the reinforcing fibers (A1), the resin (A2), and the voids (A3) constituting the porous body (A) as 100% by volume.

The density ρ of the porous body (A) is preferably 0.9 g / cm ³ or less. If the density ρ of the porous body (A) is 0.9 g / cm ³ or less, it means that the mass when the porous body (A) becomes a porous body (A) is reduced, and as a result, the weight of the porous body (A) becomes lighter, which is preferable. It is more preferably 0.7 g / cm ³ or less, and particularly preferably 0.5 g / cm ³ or less. The lower limit of the correlation density is not set, but generally a porous body (A) having reinforcing fibers (A1) and resin (A2) can be made of reinforcing fibers (A1), resin (A2), and voids from its constituent components The values calculated for the respective volume ratios of (A3) are taken as the lower limits. In the molded product of the present invention, the density of the porous body (A) itself varies depending on the reinforcing fibers (A1) and resin (A2) used. From the viewpoint of maintaining the mechanical properties of the porous body (A), It is preferably 0.03 g / cm ³ or more.

The precursor (a) of the porous body (A) of the present invention increases voids and swells with heating, and those obtained by the expansion of the voids are porous bodies (A). More specifically, the thin film layer ( B) After the formation and expansion of the former. If steps (I) and (II) of the present invention are adopted, even if the subsequent increase in voids and expansion due to heating under predetermined conditions, the precursor (a) of the present invention is still not a porous body (A). At this time, regardless of the presence or absence of voids in the precursor (a) stage, from the viewpoint that the smooth film layer (B) can be formed in step (I) or the surface quality of the obtained molded product, the voids contained in the precursor (a) The volume content ratio (A) is preferably less than 10% by volume. More preferably, the volume is less than 5% by volume, and the best quality is less than 3% by volume.

In addition, the precursor (a) preferably contains a reinforcing fiber or a foaming agent that is capable of developing swellability by applying pressure to form a compressed state. The precursor (a) more preferably contains reinforcing fibers that form a compressed state by pressing from the viewpoint of increasing the degree of freedom of the molding conditions. The reinforcing fibers are preferably of the aforementioned type or form, more preferably are discontinuous and randomly dispersed, and particularly preferably are monofilament-like and randomly dispersed. Foaming agents are: physical foaming agents that use compressed gas to release pressure or physical changes such as gas, and chemical foaming agents that generate gas by thermal decomposition or chemical reaction. Among these, a chemical foaming agent that generates nitrogen or carbonate gas by thermal decomposition is referred to as a "thermal decomposition type chemical foaming agent". Thermal decomposition type chemical foaming agent is a compound that is liquid or solid at normal temperature, and will decompose or vaporize when heated. In addition, it is preferable that the thermally decomposable chemical foaming agent does not substantially constitute an obstacle in the process of the precursor of the structural body used in the method of manufacturing the structural body of the present invention; The decomposition temperature is preferably within a range of 180 to 250 ° C.

In the porous body (A), the voids (A3) are preferably made by reducing the viscosity of the resin (A2) of the precursor (a) of the porous body (A), so that the reinforcing fibers in a compressed state under pressure ( A1) Fluffing is formed by restoring force when returning to the original state (shape before compression). In this case, since the reinforcing fibers (A1) are bonded to each other through the resin (A2), stronger compression characteristics and shape retention of the porous body (a) can be exhibited, which is preferable.

When the bending elastic modulus of the porous body (A) is Ep and the specific gravity of the porous body (A) is ρ, the bending elasticity of the porous body (A) is expressed as Ep ^1/3 ‧ρ ^-1 The modulus is preferably 3 or more. If the specific bending elastic modulus of the porous body (A) is less than 3, the bending elastic modulus is high and the state of the high specific gravity is caused. As a result, the weight reduction effect required for forming a molded article cannot be obtained, which is not preferable. The specific bending elastic modulus of general steel or aluminum is 1.5 or less, which is a very excellent specific bending elastic modulus region under these metal materials. In addition, it is preferred that the molded product such as a carbon fiber reinforced resin composite material focusing on weight reduction has a specific flexural modulus of 2.3, more preferably 3 or more, and more preferably 5 or more. The upper limit of the specific flexural modulus is not particularly limited, but it is preferably 20 or less. When the specific bending elastic modulus of the porous body (A) is greater than 20, the weight reduction effect is sufficient, but the bending elastic modulus is low, and it is difficult to maintain the shape required for forming the molded product, or the bending of the porous body itself The difference in elastic modulus is not good.

The bending elastic modulus Ep of the porous body (A) is preferably 3 GPa or more, and more preferably 6 GPa or more. If the bending elastic modulus Ep of the porous body (A) is less than 3 GPa, the range of the molded product is limited, which is not preferable. In addition, in order to facilitate the design of the porous body (A), the bending elastic modulus is preferably isotropic.

The porous body (A) of the present invention preferably has an elastic restoring force of 1 MPa or more at 50% compression. Here, the elastic restoring force is a compressive strength when the porous body (A) is compressed by 50% in the thickness direction as measured in accordance with JIS K7220 (2006). Since the elastic restoring force at the time of 50% compression in the thickness direction is 1 MPa or more, the shape retention of the molded article is excellent, and therefore, for example, it is excellent in operability when it is mounted on another member as a product. Practically, when the thickness direction of the molded product is set to the direction in which the load is applied, it can bear a slight load, and it will be deformed when a further more than a certain load is applied. Therefore, when a molded product is used as a product, The viewpoint of operator protection during installation is better. If the elastic recovery force at 50% compression is 1 MPa or more, although it does not pose a problem in practical use, it is preferably 3 MPa or more, and more preferably 5 MPa or more.

In the molded article of the present invention, the difference in expansion coefficient in the thickness direction of the porous body (A) is preferably 300% or less. When the difference in expansion ratio of the porous body (A) in the thickness direction is 300% or less, it is possible to prevent the thin film layer (B) formed on the surface of the porous body (A) from cracking or wrinkling. When determining the expansion coefficient difference of the porous body (A), first, the expansion coefficient S of the porous body (A) is determined. First, the precursor (a) after the thin film layer (B) is formed on the surface in the step (I) described later, the total thickness t1 with the thin film layer (B), and the thickness t2 of the molded article obtained in step (II) ( The total thickness of the porous body (A) and the thin film layer (B)). From the measured thickness and the following formula, the maximum expansion rate S is set to the maximum expansion rate Smax, and the minimum expansion rate S is set to the minimum expansion rate Smin.

Swelling rate S (%) = (t2 ÷ t1) × 100

The expansion rate difference is calculated from these expansion rates and the following formula.

Differential expansion rate (%) = Smax-Smin

    (Film layer (B))    

In the molded article of the present invention, the thin film layer (B) has at least any one of the functions of a primer layer, a coating film layer, and a liquid-repellent layer. Here, the primer layer means a layer having an adhesion function capable of improving the adhesion with the subsequent paint. The coating layer is a design layer that becomes the outer surface of the molded product of the final product. The liquid-repellent layer has a layer capable of preventing liquid from penetrating. When the thin-film layer is used as the outer surface of the molded product of the final product, the liquid can be prevented from penetrating into the porous body (A). The liquid that has penetrated into the porous body (A) penetrates to impart the function of storage.

In the molded article of the present invention, the film layer (B) preferably has an additive (B1) and a thermosetting resin (B2), or has an additive (B1) and a thermoplastic resin (B3).

The additive (B1) is added for the purpose of imparting design properties such as coloring, pearly luster, or metallic feeling to a molded article.

Examples of the additive (B1) include pigments and glass beads. Specific examples include organic pigments such as azo pigments and phthalocyanine blue; metal pigments composed of metal powders such as aluminum and brass; and inorganic pigments such as chromium oxide and cobalt blue. Among them, metal pigments and inorganic pigments are preferred from the viewpoint of heat resistance. Further, in the case of dark colors such as reinforcing fiber-based carbon fibers or polyaramide fibers, it is preferable to use a pigment having two or more layers of structures having different refractive indices. For example: natural mica coated with titanium oxide or iron oxide, artificial mica, alumina fragments, silicon dioxide fragments, glass fragments. With such a layer structure, color can be developed by utilizing optical phenomena such as interference, diffraction, and scattering of light in the visible region. If optical phenomena such as interference, diffraction, and scattering of light are used, the color can be developed by reflection of light of a specific wavelength, so it can be preferably used when dark-colored reinforcing fibers are used.

In addition, from the viewpoint of suppressing an increase in the mass of the film layer (B) and the molded product, it is preferable to use a hollow-shaped additive (B1). In particular, from the viewpoint of weight reduction, hollow glass beads, porous resin particles, and the like are preferred.

The additive (B1) may be in the form of a sphere, a fiber, or a chip. The maximum size of the additive (B1) is preferably 200 μm or less. The "maximum size of the additive (B1)" herein means the maximum diameter of the primary particles of the additive (B1), or the maximum diameter of the secondary particles when the additive (B1) is agglomerated. When the maximum size of the additive (B1) is 200 μm or less, the surface of the thin film layer (B) becomes smooth, and the design is improved. The maximum size of the additive (B1) is the observation of the additive using an electron microscope. From the image enlarged to a size of at least 1 μm, any 100 additives (B1) are randomly selected, and will be randomly determined according to the outer contour of each additive (B1). The length at which the distance between the two places becomes the maximum is taken as the average of the measured values of the maximum length.

The maximum size of the additive (B1) is more preferably 150 μm, and particularly preferably 100 μm. The lower limit of the maximum size of the additive (B1) is preferably 1 μm, more preferably 5 μm, and particularly preferably 10 μm.

In the film layer (B) of the present invention, the thermosetting resin (B2) contains a thermosetting resin (B2) and a curing agent (B2 '). The thermosetting resin (B2) is not particularly limited, and any thermosetting resin (B2) such as an epoxy resin, an unsaturated polyester, or a phenol resin can be used. The thermosetting resin (B2) can be used alone or can be blended appropriately. When using the additive (B1) which imparts design property, it is preferable to use an epoxy resin or an unsaturated polyester with high transparency.

Hardeners (B2 ') are, for example, compounds that undergo stoichiometric reactions such as aliphatic polyamines, aromatic polyamines, dicyandiamide, polycarboxylic acids, polycarboxylic acid hydrazines, acid anhydrides, polythiols, and polyphenols, and Compounds that act as catalysts, such as imidazole, Lewis acid complexes, and onium salts. When a compound that undergoes a stoichiometric reaction is used, the hardening accelerator may be further formulated such as imidazole, Lewis acid complex, onium salt, urea derivative, phosphine, and the like. In the hardener (B2 '), from the viewpoint of excellent heat resistance or mechanical properties of the obtained molded product, it is preferred to use a molecule containing nitrogen, such as amine group, amidine amino group, imidazole group, urea group, and hydrazine group. Atomic organic nitrogen compounds. The hardener may be used alone or in combination.

In the film layer (B) of the present invention, the thermoplastic resin (B3) is not particularly limited, and any thermoplastic resin such as an acrylic resin, an amine ester resin, a polyamide resin, a polyimide resin, or a vinyl chloride resin can be used. Resin (B3). The thermoplastic resin (B3) can be used alone, or it can be blended appropriately. The thermosetting resin (B2) and the thermoplastic resin (B3) can be selected similarly to the resin (A2) constituting the porous body (A).

When the additive (B1) of the thin film layer (B) is a pigment and has a thermosetting resin (B2), the refractive index difference between the pigment and the thermosetting resin (B2) cured product is preferably 0.1 or less. The smaller the refractive index difference, the more the transparency of the thin film layer (B) is improved, and therefore the coloring effect of the pigment can be strongly developed.

The state of materials forming the thin film layer (B) can be classified into a solution system, a dispersion system, and a powder system. The solution system is one in which the main element forming the thin film layer (B) is dissolved in a solvent, and the solvent is in the form of an organic solvent or water. A dispersion system is one in which the main elements forming the thin film layer (B) are dispersed in a solvent to form an emulsified state, which is also called an emulsion type. The powder system is a powder form which is composed of a solid content without using a solvent. From the viewpoint of the ease of operation in step (I), it is preferably a solution system and a dispersion system. From the viewpoint of the operating environment, the solvent is preferably water. From the viewpoint of the formation time of the thin film layer (B), the solvent is preferably organic. Solvent.

    (Molded product)    

In the molded article of the present invention, the thickness of the thin film layer (B) is preferably 10 μm or more and 500 μm or less. If the thickness is less than 10 μm, it may be difficult to maintain the shape of the thin film layer (B) when it is formed on the porous body (A) in the step (II). Further, if the thickness is more than 500 μm, a smooth surface or a surface having excellent design properties can be formed, but the molding quality is increased, and it is difficult to express the lightweight of the molded product. The thickness of the thin film layer (B) is more preferably 400 μm or less, and particularly preferably 300 μm or less. In addition, when the thin film layer (B) is provided on both the surface of the porous body (A) and the other surface, the thickness of the thin film layer (B) refers to the individual thickness of each thin film layer (B), and is preferably located at The thickness of the thin film layer (B) of at least one outer layer of the porous body (A) is within the above range, and more preferably the thickness of the thin film layer (B) of the two outer layers is within the above range, respectively.

In the molded article of the present invention, the surface roughness Ra2 of the thin film layer (B) is preferably 100 m or less. When the surface roughness Ra2 is 100 μm or less, the surface can be smoothed, and a molded product having more excellent design properties can be obtained. When the thin film layer (B) is an adhesive layer, when considering not only chemical bonding but also mechanical bonding (anchoring), the surface roughness Ra2 is preferably 30 μm or more. On the other hand, when it is a coating film layer, from a design viewpoint, it is preferable that surface roughness Ra2 is 50 micrometers or less.

The density ρ of the molded product of the present invention is preferably 1.0 g / cm ³ or less. When the density ρ of the molded product is 1.0 g / cm ³ or less, the mass of the molded product is reduced, that is, it contributes to weight reduction when it becomes a product, which is preferable. More preferred is 0.8 g / cm ³ or less, and particularly preferred is 0.6 g / cm ³ or less. The lower limit of the relevant density is not set. If a porous body (A) containing reinforcing fibers (A1) and a resin (A2) is generally provided, and an additive (B1) and a thermosetting resin (B2) or a thermoplastic resin are provided, (B3) A formed article of the thin film layer (B), from the reinforcing fibers (A1), resin (A2), voids (A3), additives (B1), thermosetting resin (A2), and The calculated value of the respective volume ratios of the thermoplastic resin (A3) can be regarded as the lower limit. In the molded product of the present invention, the density of the molded product varies depending on the reinforcing fiber (A1), resin (A2), etc. used. From the viewpoint of maintaining the mechanical characteristics of the molded product, it is preferably 0.05 g / cm ³ the above.

The method for producing the precursor (a) is, for example, a method in which a resin in a molten or softened state on a reinforcing fiber felt is subjected to pressure or pressure reduction to melt-impregnate the resin. Specifically, from the viewpoint of ease of production, a method in which a resin laminate is disposed on both sides and / or the center of the reinforcing fiber felt in the thickness direction, and a method in which the resin is melt-impregnated by applying heat and pressure is exemplified.

In addition, as long as the formation of the thin film layer (B) in the step (I) is not hindered, the step of expanding the precursor (a) in advance or the step of forming the target shape of the molded product in advance may be performed.

    (Prefabricated products)    

The preform of the formed product of the present invention is a preform of a formed product forming a thin film layer (B) on the surface of a porous body (A) provided with reinforcing fibers (A1), resin (A2), and voids (A3); Among them, the precursor (a) of the porous body (A) and the thin film layer (B) on the surface of the precursor (a) are provided, and the thin film layer (B) is based on JIS K5600-5-6 (1999). The adhesion to the aforementioned precursor (a) belongs to the classifications 0 to 3.

By using such a preform, it is possible to prevent the thin film layer (B) from excessively penetrating into the porous body (A), and it is possible to reduce the weight of the product. In addition, when the precursor (a) is expanded to form the porous body (A), peeling of the thin film layer (B) can be suppressed, and the shape and traceability of shapes such as a mold are also excellent. Moreover, even if the step (II) of the forming step is performed at a place different from the step (I), the preform of the molded article of the present invention has a porous body (A) precursor (a) and a thin film layer (B). It adheres in a state with a predetermined adhesiveness. Therefore, it is not necessary to laminate the precursor (a) and the thin film layer (B) during the forming step, and it is also excellent in handling properties. Therefore, a molded product can be easily manufactured.

    (Manufacturing method of molded products)    

In the method for manufacturing a molded article of the present invention, a thin film layer (B) is first formed on the surface of the precursor (a) of the porous body (A), and a preform is obtained (step (I)).

The method for producing the precursor (a) may be, for example, a method of applying pressure or decompression to a resin (A2) in a molten or softened state and having a fluid state on a reinforcing fiber mat made of reinforcing fibers (A1). . Specifically, from the viewpoint of ease of production, it is preferable to exemplify the resin (A2) by heating and pressing the laminate in which the resin (A2) is disposed on both sides and / or the center of the thickness direction of the reinforcing fiber felt. Melt impregnation method.

The manufacturing method of the reinforcement fiber mat which comprises a porous body (A) is the method of manufacturing a reinforcement fiber mat by dispersing the reinforcement fiber (A1) in the shape of a strand and / or a monofilament, for example. For example, a known technique of a method for manufacturing a reinforced fiber felt is an air-laid method in which reinforcing fibers (A1) are dispersed and thinned by an air stream; the reinforcing fibers (A1) are mechanically combed and shaped while being shaped. A dry process such as a thin carding method is performed; a wet process is performed by a Rodoraito method in which a reinforcing fiber (A1) is stirred in water to perform papermaking. Means for making the reinforcing fiber (A1) closer to a monofilament, and the dry process system can be exemplified by a method of setting a fiber opening rod or a method of vibrating the fiber opening rod, a method of reducing a card opening mesh, or adjusting a card rotation Speed method, etc. The wet process system can be exemplified by a method of adjusting the stirring conditions of the reinforcing fibers (A1), a method of diluting the concentration of the reinforcing fibers of the dispersion, a method of adjusting the viscosity of the dispersion, and a method of suppressing vortex flow when the dispersion is transferred. The reinforced fiber mat is particularly preferably manufactured by a wet process. By increasing the concentration of the input fiber, or adjusting the flow rate (flow rate) of the dispersion and the speed of the mesh conveyor, the reinforcing fiber of the reinforced fiber mat can be easily adjusted. (A1) ratio. For example, by making the speed of the mesh conveyor relatively slower than the flow rate of the dispersion liquid, the fiber orientation in the obtained reinforcing fiber mat cannot be easily oriented in the stretching direction, and a fluffy reinforcing fiber mat can be manufactured. Reinforced fiber mats can be composed of reinforced fiber monomers. The reinforcing fibers (A1) can be mixed with powder or fiber-shaped matrix resin components, or the reinforcing fibers (A1) can be mixed with organic or inorganic compounds, or A1) The resin components are filled with each other.

The equipment for implementing the above methods is preferably a compression molding machine or a two-belt press. In the case of batch type, the former is adopted. By forming an intermittent press system with two or more heating and cooling side by side, productivity can be improved. In the case of the continuous type, the latter is adopted because continuous processing can be easily performed, and thus continuous productivity is excellent.

In step (I), a thin film layer (B) is formed on the surface of the precursor (a) formed as described above. The method for forming the thin film layer (B) is not particularly limited, as long as the thin film layer (B) can be formed for the purpose. For example, dry coating such as electroplating, wet coating using a solution, etc., and a method of modifying the surface of the precursor (a) to form a thin film layer (B). Among them, the thin film layer (B) is preferably formed by wet coating. Coating methods include, for example, brush coating, roller coating, spray coating, airless spraying, roller coating, baking paint coating, dip coating, electrodeposition coating, electrostatic coating, powder Coating, UV curing coating, etc. If the treatment is performed at a high temperature, it is preferably applied by baking paint.

In addition, the method for producing a molded article of the present invention is formed by forming a thin film layer (B) on the precursor (a), expanding the precursor (a), and forming the precursor (a) on the porous body (A). Resin in a softened state or resin with fluidity, especially in the case of low-viscosity resins used in wet coating, can still prevent the film layer (B) from penetrating into the porous body (A) excessively, and can easily obtain a film layer (B) A molded article having a thickness of 500 μm or less. Therefore, in terms of the appearance and design required for a molded article, the various coating methods as described above can be said to be a manufacturing method with a high degree of freedom in selecting a thin film layer.

The thin film layer (B) formed on the surface of the precursor (a) according to step (I) is preferably based on JIS K5600-5-6 (1999). The adhesion to the precursor (a) belongs to the classification 0 ~ 3. Since the thin film layer (B) has predetermined adhesion on the surface of the precursor (a), even if the step (II) is performed in a place different from the step (I), the thin film layer (B) can be prevented from peeling off. A molded article having excellent design properties is obtained.

Furthermore, the surface roughness Ra1 of the thin film layer (B) formed on the surface of the precursor (a) according to step (I) is preferably 50 μm or less. By setting the surface roughness Ra1 of the thin film layer (B) after step (I) to 50 μm or less, the surface roughness Ra2 of the thin film layer (B) after step (II) of the forming step can be set to a desired range Inside.

Next, the method for expanding the precursor (a) to form the porous body (A) (step (II)) is not particularly limited, and it is preferred that the precursor (a) constituting the porous body (A) be The viscosity of the resin (A2) of a) is reduced, and the resin (A) is molded on the porous body (A). The method for reducing the viscosity of the resin (A2) is preferably heating the precursor (a) of the porous body (A). The heating method is not particularly limited, and examples thereof include a method of heating by contacting a mold or a hot plate set at a desired temperature, and a method of heating by using a non-contact state such as a heater. When the resin (A2) constituting the porous body (A) is a thermoplastic resin, it is only necessary to heat it above the melting point or softening point. If a thermosetting resin is used, it depends on the temperature at which the curing reaction starts. Perform heating at a lower temperature.

The method for controlling the thickness of the porous body (A) and the molded product is based on the premise that the heated precursor (a) can be controlled to the target thickness. The method is not limited. From the viewpoint of manufacturing simplicity, it is preferable The method is exemplified by a method of using a metal plate or the like to constrain the thickness; a method of controlling the thickness by using the pressure given by the precursor (a); and the like. The equipment for implementing the above method is preferably a compression molding machine or a two-belt press. In the case of batch type, the former is adopted. By forming an intermittent press system with two or more heating and cooling side by side, productivity can be improved. In the case of the continuous type, the latter is adopted because continuous processing can be easily performed, and thus continuous productivity is excellent.

Furthermore, the method for manufacturing a molded article of the present invention preferably includes the step (III) which is performed simultaneously with the step (II) or after the step (II) and deforms the shape of the porous body (A). . Step (III) can be carried out by forming a shape by applying pressure in a heated state.

The molded article of the present invention manufactured as described above is applicable to, for example, "a personal computer, a monitor, an OA device, a mobile phone, a mobile information terminal, a PDA (mobile information terminal such as an electronic notebook), a video camera, an optical device, and an audio device. , Air conditioners, lighting equipment, entertainment supplies, toy supplies, other household appliances, etc., housings, brackets, cabinets, interior components, vibration plates, speaker cones, or their boxes "and other electrical and electronic machine parts;" "Speaker cone" and other acoustic components; "various components, various frames, various hinges, various arms, various axles, various wheel bearings, various beams", "covers, roofs, doors, fenders, car trunks, side panels , Rear panel, front car shell, chassis, various pillars, various components, various frames, various beams, various brackets, various slide rails, various hinges "and other outer panels, or body parts;" bumpers, bumper beams, Exterior parts such as trims, underbody shields, hoods, fairings, spoilers, front cover vents, aero kits, etc .; "dashboards, frame, door trims, pillars Boards, handles, various modules "and other built-in parts; or" motor parts, CNG tanks, gasoline tanks "and other structural parts for automobiles and two-wheelers;" battery trays, headlight stands, pedal housings, protectors, light reflectors , Lamp housing, noise canceling board, spare tire cover "and other automotive and motorcycle parts;" wall interior components such as sound insulation walls, soundproof walls "and other building materials;" landing gear, wing warp, spoiler, flange, ladder, elevator , Fairings, ribs, seats "and other aircraft parts. From the viewpoint of mechanical characteristics and shapeability, it is preferably used in automobile interior and exterior, electrical and electronic equipment housings, bicycles, structural materials for sporting goods, aircraft interior materials, transportation boxes, and building materials.

    [Example]    

Hereinafter, the present invention will be specifically described using examples.

    (1) Volume content Vf of reinforcing fibers in the porous body (A) of the molded product    

Only the porous body (A) was cut out of the molded article as a test piece, and after measuring the mass Ws, the test piece was heated at 500 ° C for 30 minutes in the air to burn out the resin (A2) component and measure the remaining reinforcing fibers (A1) The mass Wf is calculated according to the following formula. At this time, the densities of the reinforcing fibers (A1) and the resin (A2) were measured using a hydrostatic specific gravity measurement method according to JIS Z8807 (2012).

Vf (volume%) = (Wf / ρf) / (Wf / ρf + (Ws-Wf) / ρr) × 100

ρf: density (g / cm ³ ) of the reinforcing fiber (A1)

ρr: density (g / cm ³ ) of resin (A2)

    (2) Density ρ of the porous body (A) of the molded product    

Only a portion of the porous body (A) was cut out from the molded article as a test piece, and the apparent density of the porous body (A) was measured with reference to JIS K7222 (2005). The size of the test piece was 100 mm in length and 100 mm in width. The length, width, and thickness of the test piece were measured using a micrometer, and the volume V of the test piece was calculated from the obtained values. The mass M of the cut test piece was measured with an electronic balance. By substituting the obtained mass M and volume V into the following formula, the density ρ of the porous body (A) was calculated.

ρ [g / cm ³ ] = M [g] / V [cm ³ ]

    (3) Density of molded product ρm    

A portion containing the porous body (A) and the thin film layer (B) was cut out from the molded product as a test piece, and the apparent density of the molded product was measured in the same manner as the density ρ of the porous body (A) of the molded product. Calculate the density ρm.

    (4) Volume content ratio of the precursor (a) of the porous body (A) and the void (A3) of the porous body (A)    

A test piece with a length of 10 mm and a width of 10 mm was cut out from the porous body (A) or precursor (a), and the cross section was observed with a scanning electron microscope (SEM) (S-4800 type manufactured by Hitachi High-Technologies Co., Ltd.). On the surface of the film, 10 places were photographed at equal intervals at a magnification of 1000 times. For each image, the area Aa of the gap (A3) in the image is obtained. The void ratio was calculated by dividing the area Aa of the void (A3) by the entire image area. The volume content of the voids of the porous body (A) or the precursor (a) was obtained by taking an average of the void ratios of 50 locations for each of the five test pieces.

    (5) Adhesion of thin film layer (B) to precursor (a) of porous body (A)    

The adhesion of the thin film layer (B) was evaluated in accordance with JIS K5600-5-6 (1999) General Test Method for Coatings-Mechanical Properties of the Coating Film-Adhesion (Cross Cut Method). The sample was observed with a laser microscope (Keyence Corporation, VK-9510) at a magnification of 400 times. The observation image is developed on the general image analysis software, and the area of the film layer (B) peeled off in the observation image is obtained by using a program matched with the software. The test results in Table 1 of JIS K5600-5-6 were classified as 0 to 3 and rated as "good", and 4 to 5 were rated as "not good".

    (6) Maximum size of additive (B1) in film layer (B)    

The shape of the additive (B1) was measured using a laser microscope. The measurement of the maximum size of the additive (B1) can be assumed to be: the measurement of the additive (B1) alone, the measurement after mixing with the resin (A2) and in a fluid state, the measurement after mixing with the resin (A2), and without Measurement in a fluid state (hardened or cured state). Additives (B1) and fluidity can be measured directly in their original state. In the case of no fluidity, it is embedded with epoxy resin, the cross section is observed after grinding, and then the maximum size is measured.

    (7) Thickness of film layer (B)    

A test piece having a length of 10 mm and a width of 10 mm was cut out from the molded product, and the film layer (B) was measured using a laser microscope in the same manner as (5) the adhesion of the film layer (B) to the precursor (a) of the porous body (A). thickness of. Ten positions were taken at regular intervals from the end in the thickness direction of the sample piece, and the position of the porous body (A) side was measured from the surface of the film layer (B). The thickness of the thin film layer (B) was obtained by taking 10 places on 5 test pieces, and the thickness of the thin film layer (B) from 50 places was calculated by arithmetic mean.

(8) Surface roughness Ra1 and Ra2 of the thin film layer (B)

For the thin film layer (B) formed in step (I) and the thin film layer (B) of the molded product, use a surface roughness meter to select a cutoff value and a reference length in accordance with JIS-B-0601 (2001), and determine the surface roughness Ra1 (μm) and Ra2 (μm).

    (9) Poor body (A) Difference in expansion ratio in thickness direction    

After the thin film layer (B) is formed in step (I), the total thickness t1 of the precursor (a) and the thin film layer (B) is measured, and then the thickness t2 (the porous body (A) of the molded article formed in the step (II) is measured. ) And the thickness of the thin film layer (B)). From the measured thickness and the following formula, the maximum expansion rate S is set to the maximum expansion rate Smax, and the minimum expansion rate S is set to the minimum expansion rate Smin.

Swelling rate S (%) = (t2 + t1) × 100

The expansion rate difference is calculated from these expansion rates and the following formula.

Differential expansion rate (%) = Smax-Smin

    (10) Air permeability of porous body (air permeability in thickness direction)    

The air permeability of the porous body (A) was measured in accordance with the following (a) to (d). Ventilators whose JIS specifications are up to 500 Pa up to the upper limit of the test conditions are judged to be "ventilative", and others are judged to be "non-ventilable".

(a) Cut out a test piece of 100 mm × 100 mm and thickness 5 mm from the porous body (A) (if it is 5 mm or less, use it directly. If it is thicker than 5 mm, it is convenient to adjust the thickness by cutting or the like).

(b) 4 sides of the end portion (cutting surface) of the test piece are covered with an adhesive tape (to prevent ventilation in the thickness direction and the vertical direction).

(c) A test piece is attached to one end of a testing machine cylinder that can be measured by JIS L1096 (2010) method A (Frazier method).

(d) Adjust the exhaust fan and air holes so that the tilt barometer becomes a pressure below 500Pa.

    (11) Bend test    

A test piece was cut out from the formed body, and the bending elastic modulus was measured according to the ISO178 method (1993). The measurement number was set to n = 5, and the arithmetic mean value was set to the bending elastic modulus Ec. The measuring device was an "INSTRON (registered trademark)" 5565 universal material testing machine (INSTRON ‧ Japan). From the obtained results, the specific bending elastic modulus of the molded body was calculated from the following formula.

Specific bending elastic modulus = Ec ^1/3 / ρ

In the following examples and comparative examples, the following materials were used.

    [Reinforced fiber felt 1]    

The Torayca T700S-12K made by Toray Co., Ltd. was cut into 5mm with a utility knife to obtain cut carbon fiber. A dispersion of 0.1% by mass consisting of water and a surfactant (manufactured by NACALAI TESQUE (poly), polyoxyethylene lauryl ether (trade name)) was prepared, and the dispersion was used to cut carbon fiber, and shown in Figure 2 Reinforced fiber felt manufacturing apparatus manufactures a reinforced fiber felt. The manufacturing apparatus shown in FIG. 2 includes a dispersion tank having a cylindrical container with a diameter of 1000 mm and an open cock at the bottom of the container, and a linear conveying section (inclination angle of 30 °) connecting the dispersion tank and the papermaking tank. ). A mixer is attached to the opening on the upper surface of the dispersion tank, and the cut carbon fiber and the dispersion liquid (dispersion medium) can be thrown into the opening. The papermaking tank is provided with a mesh conveyor having a bottom paper width of 500mm, and a conveyor capable of conveying a carbon fiber substrate (papermaking substrate) is connected to the mesh conveyor. The papermaking system is implemented by setting the carbon fiber concentration in the dispersion to 0.05% by mass. The paper-made carbon fiber substrate was dried in a 200 ° C drying oven for 30 minutes to obtain a reinforcing fiber felt 1 having an apparent density of 100 g / m ² .

    [PP resin]    

80% by mass of unmodified polypropylene resin ("Prime Polyρro" (registered trademark) J105G made by Prime Polymer Co., Ltd.) and 20 masses of acid-modified polypropylene resin ("ADMER" QB510 made by Mitsui Chemicals Co., Ltd.) % Resin sheet with an apparent density of 200 g / m ² .

    [Paint 1]    

Paint 1 is prepared with "naxPP primer" made by Japan Paint Co., Ltd. Coating 1 contains a thermoplastic resin and has the function of a primer layer.

    [Paint 2]    

Paint 2 is prepared with "Creative Color Spray" made by Asahipen. Coating 2 contains a thermoplastic resin and has the function of a coating layer.

    [Paint 3]    

The paint 3 was prepared in accordance with jER828: 100 parts by mass of the main agent system of Mitsubishi Chemical Co., Ltd., and 11 parts by mass of the hardening agent of 11 parts of triethylene glycol tetraamine produced by Tokyo Chemical Industry Corporation. Coating 3 contains a thermosetting resin and has a liquid-repellent layer.

    [Additive 1]    

Additive 1 was prepared with 3M glass microspheres K20 (bulk density: 0.13 g / cm ³ , median particle size: 60 μm).

    [Precursor (a) of porous body (A)]    

Reinforced fiber felt uses reinforced fiber felt 1 and resin sheet uses PP resin, and is produced in the order of [resin sheet / reinforced fiber felt / resin sheet / reinforced fiber felt / reinforced fiber felt / resin sheet / reinforced fiber felt / resin sheet] Configuration of laminates. Next, the precursor (a) of the porous body (A) is obtained through the following steps (1) to (4).

Step (1): The laminate is placed in a die-forming cavity preheated to 200 ° C, and then the die is closed.

Step (2): Next, a pressure of 3 MPa was applied and held for 180 seconds.

Step (3): After step (2), cool the cavity temperature to 50 ° C while maintaining the pressure.

Step (4): Open the mold and take out the precursor (a).

    (Example 1)    

The above step (I) is performed on the surface of the precursor (a) of the porous body (A), and the coating material 1 is spray-coated three times. After 30 minutes of drying, the precursor material (a) is formed of the coating material 1 Thin film layer (B) to obtain a preform. Table 1 shows the surface roughness Ra1 and adhesion of the film layer (B) of the obtained preform.

Next, the preform is obtained in the above step (II) through the following steps (II-1) to (II-5) to obtain a molded article. Table 1 shows the characteristics of the molded article obtained in Example 1.

Step (II-1): The preform is placed in a die-forming cavity preheated to 200 ° C, and then the die is closed.

Step (II-2): After holding for 120 seconds, a pressure of 3 MPa was applied, and the pressure was further maintained for 60 seconds.

Step (II-3): The mold cavity is opened, and a metal spacer is inserted at the end thereof to adjust the thickness at the time of obtaining a molded product to 3.4 mm.

Step (II-4): The mold cavity is screw-locked, and the temperature of the cavity is cooled to 50 ° C. while the pressure is maintained.

Step (II-5): Open the mold and take out the molded product.

    (Example 2)    

Coating 2 was spray-coated twice on the surface of precursor (a), and after drying for 1 hour, a thin film layer (B) composed of coating 2 was formed on precursor (a) to obtain a preform. Table 1 shows the surface roughness Ra1 and adhesion of the film layer (B) of the obtained preform.

Next, the obtained preform was subjected to steps (II-1) to (II-5) in the same manner as in Example 1 to obtain a molded product. Table 1 shows the characteristics of the molded article obtained in Example 2.

    (Example 3)    

Coating 3 was applied once on the surface of precursor (a) using a roller, and dried for 1 hour in a dryer set at a temperature of 50 ° C in the furnace to form a coating composed of coating 3 on precursor (a). Thin film layer (B) to obtain a preform. Table 1 shows the surface roughness Ra1 and adhesion of the film layer (B) of the obtained preform.

Next, the obtained preform was subjected to steps (II-1) to (II-5) in the same manner as in Example 1 to obtain a molded product. Table 1 shows the characteristics of the molded article obtained in Example 3.

    (Example 4)    

Additive 1:15 weight part was added to the coating material 3, and the coating material 4 was prepared. Except that the coating material 4 was used, in the same manner as in Example 3, a thin film layer (B) composed of the coating material 4 was formed on the precursor (a) to obtain a molded product. Table 1 shows the surface roughness Ra1 and adhesion of the obtained thin film layer (B), and the characteristics of the molded article obtained in Example 4.

    (Example 5)    

A molded product was obtained in the same manner as in Example 1 except that the precursor (a) was placed in a mold shown in FIG. 3 to obtain a molded product. Table 1 shows the surface roughness Ra1 and adhesion of the obtained thin film layer (B), and the characteristics of the molded article obtained in Example 5. In addition, in FIG. 3, 4 is a precursor (a), 5 is a thin-film layer (B) made of paint 1, 3A is an upper mold, and 3B is a lower mold.

    (Example 6)    

A preform in which a thin film layer (B) was formed on the surface and a mold (3A, 3B) having an unevenness difference of 0.6 mm as shown in FIG. 4 were prepared. Next, the above step (II) is to obtain a molded product through the following steps (II-6) to (II-10). Table 1 shows the characteristics of the molded article obtained in Example 6.

Step (II-6): The preform is placed in an IR heater set at 250 ° C.

Step (II-7): After heating for 60 seconds, the preform is placed in a mold set at a temperature of 120 ° C., a pressure of 3 MPa is applied, and it is held for 5 seconds.

Step (II-8): Open the die cavity, insert a metal spacer at its end, and adjust the thickness of the concave portion of the molded product to 3.4 mm.

Step (II-9): The screw lock mold cavity is held for 180 seconds while maintaining the pressure.

Step (II-10): Open the mold and take out the molded product.

    (Example 7)    

A molded article was obtained in the same manner as in Example 6 except that a mold having an unevenness of 3.6 mm shown in FIG. 4 was prepared. Table 1 shows the characteristics of the molded article obtained in Example 7.

    (Example 8)    

A molded article was obtained in the same manner as in Example 1 except that a fluorine-based release agent was applied to the surface of the precursor (a) of the porous body (A) and then the coating material 1 was applied. Table 1 shows the surface roughness Ra1 and adhesion of the obtained thin film layer (B), and the characteristics of the molded article obtained in Example 8.

    (Example 9)    

Except that the same material as in Example 1 was used, and in step (3) of obtaining the precursor (a) of the porous body (A), the thickness of the precursor (a) was adjusted to 1.24 mm. In Example 1, a molded product was obtained in the same manner. Table 1 shows the characteristics of the molded article obtained in Example 9.

    (Comparative example 1)    

In a state where the thin film layer (B) was not formed on the surface of the precursor (a), a porous body (A) was obtained in the same manner as in Example 1. About the obtained porous body (A), it carried out similarly to Example 1, and formed the thin film layer (B) which consists of the coating material 1, and obtained the molded article. Table 2 shows the surface roughness Ra1 of the obtained thin film layer (B), the adhesion, and the characteristics of the molded article obtained in Comparative Example 1.

    (Comparative example 2)    

Except that the precursor (a) of the porous body (A) was superposed three times and the holding time of step (II) was set to 600 seconds, steps (II-1) were performed in the same manner as in Example 1. In step (II-5), a void-free formed article is obtained. About the obtained molded object, the thin film layer (B) which consists of the coating material 1 was formed like Example 1, and the molded article was obtained. Table 2 shows the surface roughness Ra1 of the obtained thin film layer (B), adhesion, and characteristics of the molded article obtained in Comparative Example 2.

    [Review]    

In Examples 1 to 5, the thin film layer (B) was formed on the precursor (a) of the porous body (A) in advance, and then the porous body (A) was swelled, so that smoothness was easily obtained and the coating was not excessive. A molded article excellent in lightness of penetration. In Example 1, since the thin film layer (B) has adhesiveness, the adhesion of the subsequent design paint is excellent. In Example 2, since the film layer (B) is a coating film layer on the design surface of the final product, the obtained molded product can be immediately used as a product, and a general coating step can be omitted. In Example 3, since the thin film layer (B) is a coating material 3 made of a thermosetting resin (B2), a molded article can be obtained that maintains high surface smoothness after expansion. In addition, in Example 4, since hollow glass beads were added to the coating material 4 as an additive (B1), a molded article having excellent lightness was obtained compared with the case where a general additive (B1) was used. In Examples 5 to 7, it was confirmed that the 3-dimensional shape shaping required for the molded product can still be adapted. In Example 7, a molded product having a maximum thickness greater than that of the molded product obtained in Example 6 (with a large difference in expansion coefficient) was obtained. It was found that the use of the thickness effect can exhibit high rigidity when the molded product is used as a structural member. In addition, since a molded article having a large unevenness difference (large difference in expansion coefficient) can be obtained, the degree of freedom of the molded shape is high. On the other hand, since the difference in expansion ratio exceeds the preferable, unevenness in the thickness of the thin film layer (B) partially occurs at the convex portion of the molded article. In Example 8, although the impregnation of the thin film layer (B) was suppressed, the porous body (A) and the thin film appeared due to the lack of adhesion between the precursor (a) of the porous body (A) and the thin film layer (B). Layer (B) is a separated part. Example 9 is an example using a precursor (a) of a porous body (A) that simulates a void containing insufficient impregnation of the resin (A2). If the porosity of the precursor (a) is 10% or less, a smooth and coating material can be obtained A molded article with excellent lightweight properties without excessive penetration. On the other hand, in Comparative Example 1, since the coating material 1 was applied to the porous body (A), the coating material penetrated into the molded article (porous body), and it was difficult to form a smooth coating film. In addition, it was found that if the same thin film layer (B) 1 as that of Example 1 is to be formed, several layers of coating must be overlapped and applied, resulting in an increase in coating steps and weight. In Comparative Example 2, since a coated body was coated without a void, a smooth coating film could be formed, but the molded product was inferior in lightness.

    (Industrial availability)    

According to the present invention, a molded product having excellent rigidity and lightness, and having design properties and liquid repellency can be manufactured in a simple process.

Claims (17)

    A method for manufacturing a molded product is a method for manufacturing a molded product in which a thin film layer (B) is formed on a surface of a porous body (A), and is implemented in the order of the following steps (I) to (II): Step (I): A step of obtaining the preform by forming the thin film layer (B) on the surface of the precursor (a) of the porous body (A); step (II): expanding the precursor (a) to form the porous body (A).         The method for manufacturing a molded article according to claim 1, wherein, in the preform obtained in step (I), the adherence of the film layer (B) to the precursor (a) according to JIS K5600-5-6 (1999) The sex line belongs to the classification 0 ~ 3.         The method for manufacturing a molded article according to claim 1, wherein the thin film layer (B) is at least any one of a primer layer, a coating film layer, and a liquid-repellent layer.         The method for manufacturing a molded article according to claim 1, wherein in the step (I), the thin film layer (B) is formed on the surface of the precursor (a) by wet coating.         The method for producing a molded article according to claim 1, wherein the thin film layer (B) contains an additive (B1) and a thermosetting resin (B2).         The method for producing a molded article according to claim 1, wherein the film layer (B) contains an additive (B1) and a thermoplastic resin (B3).         The method for manufacturing a molded article according to claim 5 or 6, wherein the maximum size of the additive (B1) is 200 μm or less.         The method for manufacturing a molded article according to claim 1, wherein the thickness of the thin film layer (B) is 10 to 500 μm.         The method for manufacturing a molded article according to claim 1, wherein the surface roughness Ra1 of the thin film layer (B) formed in the step (I) is 50 μm or less.         The method for manufacturing a molded article according to claim 1, wherein the surface roughness Ra2 of the thin film layer (B) after the step (II) is 100 m or less.         The method for manufacturing a molded article according to any one of claims 1 to 10, further comprising: forming the shape of the porous body (A) at the same time as the step (II) or after the step (II) is completed. Step (III) of deformation.         The method for manufacturing a molded article according to claim 1, wherein the difference in expansion coefficient in the thickness direction of the porous body (A) is 300% or less.         The method for manufacturing a molded article according to any one of claims 1 to 12, wherein the porous body (A) contains a reinforcing fiber (A1), a resin (A2), and the void (A3).         The method for producing a molded article according to any one of claims 1 to 13, wherein the porous body (A) has voids (A3) continuous in a thickness direction.         The method for manufacturing a molded article according to claim 13, wherein in the step (II), the porous body (A) is expanded using a restoring force of the reinforcing fiber (A1).         A preform of a molded product is a preform of a molded product having a thin film layer (B) formed on a surface of a porous body (A) containing reinforcing fibers (A1), resin (A2), and voids (A3); The precursor (a) of the porous body (A) and the thin film layer (B) on the surface of the precursor (a) are provided, and the thin film layer is based on JIS K5600-5-6 (1999). (B) The adhesion to the precursor (a) belongs to classifications 0 to 3.         The preform of the molded article according to claim 16, wherein the volume content rate of the voids contained in the precursor (a) is less than 10% by volume.